Phosphogypsum has often been used as an effective and environmentally friendly binder for partial replacement of cement,improving the engineering properties of slurries with high water content.However,the influence of...Phosphogypsum has often been used as an effective and environmentally friendly binder for partial replacement of cement,improving the engineering properties of slurries with high water content.However,the influence of phosphogypsum on the physicomechnical properties of stabilized soil subjected to wettingedrying cycles is not well understood to date.In this study,the effect of phosphogypsum on the durability of stabilized soil was studied by conducting a series of laboratory experiments,illustrating the changes in mass loss,pH value and unconfined compressive strength(qu)with wettingdrying cycles.The test results showed that the presence of phosphogypsum significantly restrained the mass loss in the early stage(lower than the 4th cycle),which in turn led to a higher qu of stabilized soil than that without phosphogypsum.After the 4th cycle,a sudden increase in mass loss was observed for stabilized soil with phosphogypsum,resulting in a significant drop in qu to a value lower than those without phosphogypsum at the 6th cycle.In addition,the qu of stabilized soils correlated well with the measured soil pH irrespective of phosphogypsum content for all wettingedrying tests.According to the microstructure observation via scanning electron microscope(SEM)and X-ray diffraction(XRD)tests,the mechanisms relating the sudden loss of qu for the stabilized soils with phosphogypsum after the 4th wetting-drying cycle are summarized as follows:(i)the disappearance of ettringite weakening the cementation bonding effect,(ii)the generation of a larger extent of microcrack,and(iii)a lower pH value,in comparison with the stabilized soil without phosphogypsum.展开更多
To achieve the resource utilization of solid waste phosphogypsum(PG)and tackle the problem of utilizing potassium feldspar(PF),a coupled synergistic process between PG and PF is proposed in this paper.The study invest...To achieve the resource utilization of solid waste phosphogypsum(PG)and tackle the problem of utilizing potassium feldspar(PF),a coupled synergistic process between PG and PF is proposed in this paper.The study investigates the features of P and F in PG,and explores the decomposition of PF using hydrofluoric acid(HF)in the sulfuric acid system for K leaching and leaching of P and F in PG.The impact factors such as sulfuric acid concentration,reaction temperature,reaction time,material ratio(PG/PF),liquid–solid ratio,PF particle size,and PF calcination temperature on the leaching of P and K is systematically investigated in this paper.The results show that under optimal conditions,the leaching rate of K and P reach more than 93%and 96%,respectively.Kinetics study using shrinking core model(SCM)indicates two significant stages with internal diffusion predominantly controlling the leaching of K.The apparent activation energies of these two stages are 11.92 kJ·mol^(-1)and 11.55 kJ·mol^(-1),respectively.展开更多
The reduction of phosphogypsum(PG)to lime slag and SO_(2)using coke can effectively alleviate the environmental problems caused by PG.However,the PG decomposition temperature remains high and the product yield remains...The reduction of phosphogypsum(PG)to lime slag and SO_(2)using coke can effectively alleviate the environmental problems caused by PG.However,the PG decomposition temperature remains high and the product yield remains poor.By adding additives,the decomposition temperature can be further reduced and PG decomposition rate and product yield can be improved.However,the use of current additives such as Fe_(2)O_(3)and SiO_(2)brings the problem of increasing economic cost.Therefore,it is proposed to use solid waste copper slag(CS)as a new additive to reduce PG to prepare SO2,which can reduce the cost and meet the environmental benefits at the same time.The effects of proportion,temperature and thermostatic time on PG decomposition are investigated by experimental and kinetic analysis combined with FactSage thermodynamic calculations to optimize the roasting conditions.Finally,the reaction mechanism is proposed.It is found that adding CS to the coke and PG system can increase the rate of PG decomposition and SO_(2)yield while lowering the PG decomposition temperature.For example,when the CS/PG mass ratio increases from 0 to 1,PG decomposition rate increases from 83.38%to 99.35%,SO_(2)yield increases from 78.62%to 96.81%,and PG decomposition temperature decreases from 992.4℃to 949.6℃.The optimal reaction parameters are CS/PG mass ratio of 1,Coke/PG mass ratio of 0.06 at 1100℃for 20 min with 99.35%PG decomposition rate and 96.81%SO_(2) yield.The process proceeds according to the following reactions:2CaSO_(4)+ 0.7C + 0.8Fe_(2)SiO_(4)→0.8Ca_(2)SiO_(4)+ 0.2Ca_(2)Fe_(2)O_(5)+ 0.4Fe_(3)O_(4)+2SO_(2)+ 0.7CO_(2)Finally,a process for decomposing PG with coke and CS is proposed.展开更多
Zinc metal is a promising anode material for next-generation aqueous batteries,but its practical application is limited by the formation of zinc dendrite.To prevent zinc dendrite growth,various Zn^(2+)-conducting but ...Zinc metal is a promising anode material for next-generation aqueous batteries,but its practical application is limited by the formation of zinc dendrite.To prevent zinc dendrite growth,various Zn^(2+)-conducting but water-isolating solid-electrolyte interphase(SEI)films have been developed,however,the required high-purity chemical materials are extremely expensive.In this work,phosphogypsum(PG),an industrial byproduct produced from the phosphoric acid industry,is employed as a multifunctional protective layer to navigate uniform zinc deposition.Theoretical and experimental results demonstrate that PG-derived CaSO_(4)2H_(2)O can act as an artificial SEI layer to provide fast channels for Zn^(2+)transport.Moreover,CaSO_(4)2H_(2)O could release calcium ions(Ca^(2+))due to its relatively high Kspvalue,which have a higher binding energy than that of Zn^(2+)on the Zn surface,thus preferentially adsorbing to the tips of the protuberances to force zinc ions to nucleate at inert region.As a result,the Zn@PG anode achieves a high Coulombic efficiency of 99.5%during 500 cycles and long-time stability over 1000 hours at 1 m A cm^(-2).Our findings will not only construct a low-cost artificial SEI film for practical metal batteries,but also achieve a high-value utilization of phosphogypsum waste.展开更多
This work aimed to use oyster shell powder (OSP) as the partial replacement of Ag/TiO2 particle to obtain multifunctional β-hemihydrate gypsum.Thus,the β-hemihydrate gypsum was mixed with different contents of OSP a...This work aimed to use oyster shell powder (OSP) as the partial replacement of Ag/TiO2 particle to obtain multifunctional β-hemihydrate gypsum.Thus,the β-hemihydrate gypsum was mixed with different contents of OSP and Ag/TiO2 particle.Antibacterial and MB removal experiments were conducted to assess the antibacterial characteristic and photocatalytic activity of β-hemihydrate gypsum with Ag/TiO2 particle and OSP.Besides,the formaldehyde degradation test was carried out to evaluate its formaldehyde removal ratio.Moreover,their setting times,compressive and flexural strengths at 1,3,and 28 days were comparatively analyzed.The experimental results prove that the composite use of OSP and Ag/TiO2 particle provide feasible multifunction for the β-hemihydrate gypsum.They can further improve the bactericidal rates and exhibit extra MB removal ratios compared with the gypsum plasters with single Ag/TiO2 particle.Besides,they can increase the formaldehyde degradation ratios,and this promotion is related to the introduction of Ag/TiO2 particle.However,OSP delays the initial setting time but promotes the final setting time of β-hemihydrate gypsum,and Ag/TiO2 particle hardly affects the setting times.Furthermore,OSP reduces the strengths of plasters at 1,3,and 28 days.But in general,the composite addition of OSP and Ag/TiO2 particle increase the compressive and flexural strengths of gypsum plasters at 1,3,and 28 days.These results provide theoretical guidance for the recycling of OSP and the preparation of gypsum-based products with antibacterial and formaldehyde degradation capabilities.展开更多
After washing and curing, P is transported from the phosphogypsum to the leachate during the phosphogypsum detoxification process, providing two ideas for phosphorus recovery from phosphogypsum leachate: 1) preparatio...After washing and curing, P is transported from the phosphogypsum to the leachate during the phosphogypsum detoxification process, providing two ideas for phosphorus recovery from phosphogypsum leachate: 1) preparation of calcium hydrogen phosphate for feed;2) preparation of calcium phosphate. A ready-to-use calcium oxide slurry was used to recover P from phosphogypsum leachate at a slurry concentration of 20% and a quantitative link between calcium to phosphorus ratio and fixation rate was fitted by mixed use batch experiments, reaction kinetics and thermodynamics, and theoretical calculations were used to demonstrate that phosphorus cannot be completely reused in the preparation of calcium hydrogen phosphate. The findings demonstrated that: a) the residual phosphorus concentration was in the range of 1300 - 1500 mg/L for the preparation of type I feed grade calcium hydrogen phosphate from phosphogypsum leachate;b) the P removal effect could reach 99.99% for the preparation of calcium phosphate from phosphogypsum using the theoretical equation: fixation rate = 87.91 - 10.96(Ca/P) + 3.22(Ca/P)<sup>2</sup> (R<sup>2</sup> = 0.9954);c) The procedure follows the suggested secondary kinetics, and according to the Freundlich isothermal model, the reaction process is under the control of the chemical reaction, with a reaction index of 0.7605. This study can be used as a theoretical guide for the recovery of P from phosphogypsum leachate, the preparation of products to bring about economic by-products, and the purification of wastewater for reuse.展开更多
基金This research was financially supported by the National Natural Science Foundation of China(Grant Nos.52178328 and 52178361)the Fundamental Research Funds for the Open-end Research Fund of State Key Laboratory for Geomechanics and Deep Underground Engineering(Grant No.SKLGDUEK2114).
文摘Phosphogypsum has often been used as an effective and environmentally friendly binder for partial replacement of cement,improving the engineering properties of slurries with high water content.However,the influence of phosphogypsum on the physicomechnical properties of stabilized soil subjected to wettingedrying cycles is not well understood to date.In this study,the effect of phosphogypsum on the durability of stabilized soil was studied by conducting a series of laboratory experiments,illustrating the changes in mass loss,pH value and unconfined compressive strength(qu)with wettingdrying cycles.The test results showed that the presence of phosphogypsum significantly restrained the mass loss in the early stage(lower than the 4th cycle),which in turn led to a higher qu of stabilized soil than that without phosphogypsum.After the 4th cycle,a sudden increase in mass loss was observed for stabilized soil with phosphogypsum,resulting in a significant drop in qu to a value lower than those without phosphogypsum at the 6th cycle.In addition,the qu of stabilized soils correlated well with the measured soil pH irrespective of phosphogypsum content for all wettingedrying tests.According to the microstructure observation via scanning electron microscope(SEM)and X-ray diffraction(XRD)tests,the mechanisms relating the sudden loss of qu for the stabilized soils with phosphogypsum after the 4th wetting-drying cycle are summarized as follows:(i)the disappearance of ettringite weakening the cementation bonding effect,(ii)the generation of a larger extent of microcrack,and(iii)a lower pH value,in comparison with the stabilized soil without phosphogypsum.
基金jointly supported by the National Key Research and Development Program of China (2019YFC1905800)the National Key Research & Development Program of China (2018YFC1903500)+4 种基金the commercial project by Beijing Zhong Dian Hua Yuan Environment Protection Technology Co., Ltd. (E01211200005)the Regional key projects of the science and technology service network program (STS program) of the Chinese Academy of Sciences (KFJ-STS-QYZD-153)the Ningbo Science and Technology Innovation Key Projects (2020Z099, 2022Z028)the Ningbo Municipal Commonweal Key Program (2019C10033)the support of Mineral Resources Analytical and Testing Center, Institute of Process Engineering, Chinese Academy of Science
文摘To achieve the resource utilization of solid waste phosphogypsum(PG)and tackle the problem of utilizing potassium feldspar(PF),a coupled synergistic process between PG and PF is proposed in this paper.The study investigates the features of P and F in PG,and explores the decomposition of PF using hydrofluoric acid(HF)in the sulfuric acid system for K leaching and leaching of P and F in PG.The impact factors such as sulfuric acid concentration,reaction temperature,reaction time,material ratio(PG/PF),liquid–solid ratio,PF particle size,and PF calcination temperature on the leaching of P and K is systematically investigated in this paper.The results show that under optimal conditions,the leaching rate of K and P reach more than 93%and 96%,respectively.Kinetics study using shrinking core model(SCM)indicates two significant stages with internal diffusion predominantly controlling the leaching of K.The apparent activation energies of these two stages are 11.92 kJ·mol^(-1)and 11.55 kJ·mol^(-1),respectively.
基金financial support from the school-enterprise cooperation projects(2019-KYY-508101-0078).
文摘The reduction of phosphogypsum(PG)to lime slag and SO_(2)using coke can effectively alleviate the environmental problems caused by PG.However,the PG decomposition temperature remains high and the product yield remains poor.By adding additives,the decomposition temperature can be further reduced and PG decomposition rate and product yield can be improved.However,the use of current additives such as Fe_(2)O_(3)and SiO_(2)brings the problem of increasing economic cost.Therefore,it is proposed to use solid waste copper slag(CS)as a new additive to reduce PG to prepare SO2,which can reduce the cost and meet the environmental benefits at the same time.The effects of proportion,temperature and thermostatic time on PG decomposition are investigated by experimental and kinetic analysis combined with FactSage thermodynamic calculations to optimize the roasting conditions.Finally,the reaction mechanism is proposed.It is found that adding CS to the coke and PG system can increase the rate of PG decomposition and SO_(2)yield while lowering the PG decomposition temperature.For example,when the CS/PG mass ratio increases from 0 to 1,PG decomposition rate increases from 83.38%to 99.35%,SO_(2)yield increases from 78.62%to 96.81%,and PG decomposition temperature decreases from 992.4℃to 949.6℃.The optimal reaction parameters are CS/PG mass ratio of 1,Coke/PG mass ratio of 0.06 at 1100℃for 20 min with 99.35%PG decomposition rate and 96.81%SO_(2) yield.The process proceeds according to the following reactions:2CaSO_(4)+ 0.7C + 0.8Fe_(2)SiO_(4)→0.8Ca_(2)SiO_(4)+ 0.2Ca_(2)Fe_(2)O_(5)+ 0.4Fe_(3)O_(4)+2SO_(2)+ 0.7CO_(2)Finally,a process for decomposing PG with coke and CS is proposed.
基金financially supported by the National Natural Science Foundation of China (22279122,52042403)the Zhejiang Provincial Natural Science Foundation of China (LZ22B030004)+2 种基金the Ministry of Education,Singapore,under its Academic Research Fund Tier 1 (RG10/22)the National Institute of Education,Singapore,under its Academic Research Fund (RI 1/21 EAH)National Institute of Education,Singapore,under its Start-Up Grant (NIE-SUG4/20AHX)。
文摘Zinc metal is a promising anode material for next-generation aqueous batteries,but its practical application is limited by the formation of zinc dendrite.To prevent zinc dendrite growth,various Zn^(2+)-conducting but water-isolating solid-electrolyte interphase(SEI)films have been developed,however,the required high-purity chemical materials are extremely expensive.In this work,phosphogypsum(PG),an industrial byproduct produced from the phosphoric acid industry,is employed as a multifunctional protective layer to navigate uniform zinc deposition.Theoretical and experimental results demonstrate that PG-derived CaSO_(4)2H_(2)O can act as an artificial SEI layer to provide fast channels for Zn^(2+)transport.Moreover,CaSO_(4)2H_(2)O could release calcium ions(Ca^(2+))due to its relatively high Kspvalue,which have a higher binding energy than that of Zn^(2+)on the Zn surface,thus preferentially adsorbing to the tips of the protuberances to force zinc ions to nucleate at inert region.As a result,the Zn@PG anode achieves a high Coulombic efficiency of 99.5%during 500 cycles and long-time stability over 1000 hours at 1 m A cm^(-2).Our findings will not only construct a low-cost artificial SEI film for practical metal batteries,but also achieve a high-value utilization of phosphogypsum waste.
基金Funded by the National Natural Science Foundation of China(51878479)。
文摘This work aimed to use oyster shell powder (OSP) as the partial replacement of Ag/TiO2 particle to obtain multifunctional β-hemihydrate gypsum.Thus,the β-hemihydrate gypsum was mixed with different contents of OSP and Ag/TiO2 particle.Antibacterial and MB removal experiments were conducted to assess the antibacterial characteristic and photocatalytic activity of β-hemihydrate gypsum with Ag/TiO2 particle and OSP.Besides,the formaldehyde degradation test was carried out to evaluate its formaldehyde removal ratio.Moreover,their setting times,compressive and flexural strengths at 1,3,and 28 days were comparatively analyzed.The experimental results prove that the composite use of OSP and Ag/TiO2 particle provide feasible multifunction for the β-hemihydrate gypsum.They can further improve the bactericidal rates and exhibit extra MB removal ratios compared with the gypsum plasters with single Ag/TiO2 particle.Besides,they can increase the formaldehyde degradation ratios,and this promotion is related to the introduction of Ag/TiO2 particle.However,OSP delays the initial setting time but promotes the final setting time of β-hemihydrate gypsum,and Ag/TiO2 particle hardly affects the setting times.Furthermore,OSP reduces the strengths of plasters at 1,3,and 28 days.But in general,the composite addition of OSP and Ag/TiO2 particle increase the compressive and flexural strengths of gypsum plasters at 1,3,and 28 days.These results provide theoretical guidance for the recycling of OSP and the preparation of gypsum-based products with antibacterial and formaldehyde degradation capabilities.
文摘After washing and curing, P is transported from the phosphogypsum to the leachate during the phosphogypsum detoxification process, providing two ideas for phosphorus recovery from phosphogypsum leachate: 1) preparation of calcium hydrogen phosphate for feed;2) preparation of calcium phosphate. A ready-to-use calcium oxide slurry was used to recover P from phosphogypsum leachate at a slurry concentration of 20% and a quantitative link between calcium to phosphorus ratio and fixation rate was fitted by mixed use batch experiments, reaction kinetics and thermodynamics, and theoretical calculations were used to demonstrate that phosphorus cannot be completely reused in the preparation of calcium hydrogen phosphate. The findings demonstrated that: a) the residual phosphorus concentration was in the range of 1300 - 1500 mg/L for the preparation of type I feed grade calcium hydrogen phosphate from phosphogypsum leachate;b) the P removal effect could reach 99.99% for the preparation of calcium phosphate from phosphogypsum using the theoretical equation: fixation rate = 87.91 - 10.96(Ca/P) + 3.22(Ca/P)<sup>2</sup> (R<sup>2</sup> = 0.9954);c) The procedure follows the suggested secondary kinetics, and according to the Freundlich isothermal model, the reaction process is under the control of the chemical reaction, with a reaction index of 0.7605. This study can be used as a theoretical guide for the recovery of P from phosphogypsum leachate, the preparation of products to bring about economic by-products, and the purification of wastewater for reuse.
